CN106532032B - A kind of carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode material and preparation method thereof - Google Patents
A kind of carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode material and preparation method thereof Download PDFInfo
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- CN106532032B CN106532032B CN201710037682.7A CN201710037682A CN106532032B CN 106532032 B CN106532032 B CN 106532032B CN 201710037682 A CN201710037682 A CN 201710037682A CN 106532032 B CN106532032 B CN 106532032B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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Abstract
The invention discloses a kind of carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode materials and preparation method thereof, transfer them in polytetrafluoroethylcontainer container after butyl titanate or isopropyl titanate, lithium hydroxide and hydrogen peroxide are specially dissolved in deionized water；By calcination except the carbon cloth after glue is placed in polytetrafluoroethylcontainer container, 140 ~ 160 DEG C of 4 ~ 8h of reaction under closed environment；Carbon cloth is taken out, is dried after being rinsed with deionized water；Again in 500 ~ 700 DEG C of 3 ~ 5h of heat treatment under inert gas shielding or vacuum condition.The present invention also provides a kind of batteries using above-mentioned flexible self-supporting negative electrode material.It is easy to operate without using metal collector, conductive additive and the binder that must be used in traditional lithium-ion battery cathode preparation process as flexible self-supporting negative electrode material；With good electric conductivity, ionic conductivity, higher battery specific capacity and high rate performance；It can arbitrarily be bent, fold and stretch simultaneously.
Description
Technical field
The present invention relates to field of batteries more particularly to a kind of carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting cathode materials
Material and preparation method thereof.
Background technique
Spinel type lithium titanate (Li4Ti5O12) have that voltage platform is steady, has extended cycle life, " zero strain " and safety
The advantages that high is a kind of ideal lithium ion battery negative material, by more domestic and foreign manufacturers for developing commercialized lithium
Ion battery.However, the non-conductor as electronics, pure Li4Ti5O12Electric conductivity is very poor, and high rate performance is bad, limits its
Using.
Lithium titanate is carried out element doping, carbon coating or it is carried out organic composite with carbon material to can effectively improve it
High rate performance.For example, using natural graphite, acetylene black, active carbon, containing carbon polymer as carbon source, high-energy ball milling combination high temperature is utilized
The modes such as sintering can obtain the lithium titanate anode material of nano-scale, carbon coating or carbon doping, effectively improve its electrochemistry
Performance.However, what the above method finally obtained is still active material powder, in further battery manufacturing process there is still a need for slurry, apply
The complex process steps such as electrode slice are made in the techniques such as cloth, cutting and it is necessary to use metal collector, conductive additive and glue
Agent is tied, the cost of battery is improved.In recent years it has been reported that electrode active material can be supported on to conductive graphene paper or carbon
Above fiber cloth, and using its entirety as flexible self-supporting electrode, to avoid using metal collector, conductive additive and glue
Agent and cumbersome electrode fabrication process are tied, however, uniform load of the active material on this kind of conducting base and at high cost
The problems such as not occupying is still without very good solution.
Summary of the invention
The present invention provides a kind of load of carbon fiber original position lithium titanate nanometer sheet flexible self-supporting negative electrode material, preparation method
And load the battery of lithium titanate nanometer sheet flexible self-supporting negative electrode material in situ containing the carbon fiber, it can solve above-mentioned ask
Topic.
To achieve the above object, the present invention provides a kind of carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting cathode material
The preparation method of material, which is characterized in that prepare as follows:
S1: by carbon cloth, calcination 20min, the temperature and time can guarantee that carbon fiber is not burnt in 300 ~ 400 DEG C of air
It loses and except glue is thorough；
S2: butyl titanate or isopropyl titanate, lithium hydroxide and hydrogen peroxide are dissolved in deionized water, are then transferred to
In polytetrafluoroethylcontainer container；
S3: it is placed in above-mentioned gained carbon cloth is adherent in above-mentioned polytetrafluoroethylcontainer container, then 140 under closed environment
~ 160 DEG C of 4 ~ 8h of reaction, selected temperature range are suitble to lithium titanate nanometer sheet in the growth of carbon fiber surface, and selected time range can
For adjusting growth thickness；
S4: carbon cloth is taken out, and is dried after rinsing out surface adhesion particle with deionized water；
S5: the carbon cloth of above-mentioned drying is warm at a temperature of 500 ~ 700 DEG C under inert gas protection or under vacuum condition
3 ~ 5h of processing obtains carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode material.The heat treatment condition can guarantee titanium
Sour lithium nanometer sheet carbon fiber surface firing and avoid fiber oxidation.
Further, the carbon cloth in the S1 step is polyacrylonitrile-radical, asphaltic base, viscose glue base or phenolic aldehyde base carbon fibre
Non-woven fabrics or woven cloth.
Further, the carbon fiber in the S1 step is carried out in air except glue, 300 are warming up to from room temperature with 4 DEG C/min ~
400 DEG C, keep the temperature 20min.
Further, the molar ratio of the butyl titanate or isopropyl titanate in the S2 step, lithium hydroxide and hydrogen peroxide is 1:4
~ 5:5, this proportion can enable that organic titanium source is completely dissolved and the embedding lithium of titanium oxide is complete, and wherein the concentration of hydrogen peroxide is 30%.
Further, the dosage of the deionized water in the S2 step be every 2 ml butyl titanate be added deionized water 50 ~
70ml, this concentration can guarantee that lithium titanate has preferable nanometer sheet pattern.
Further, the inert gas in the S5 step is argon gas or nitrogen, from room temperature to 500 ~ 700 DEG C of heating rate
For 2 DEG C/min, the heating rate be for avoid as heat up it is too fast caused by thermal stress cause falling off for lithium titanate nanometer sheet.
Another aspect, is received the present invention also provides a kind of by the carbon fiber loaded lithium titanate that the preparation method obtains
Rice piece flexible self-supporting negative electrode active material, which is characterized in that the flexible self-supporting negative electrode material include carbon fiber and its
The lithium titanate nanoscale twins of surface in situ growth, extend to 8h from 4h by the hydro-thermal reaction time, the lithium titanate nanoscale twins thickness
It is 0.2 ~ 0.6 μm, and does not need using metal collector and binder；
Another aspect, the present invention also provides a kind of battery, including anode, cathode and electrolyte, which is characterized in that institute
Stating cathode includes according to the carbon fiber loaded lithium titanate nanometer sheet negative electrode active material；The carbon fiber loaded lithium titanate nanometer
The lithium titanate nanoscale twins of piece negative electrode active material are evenly coated at carbon fiber surface.
1) for lithium titanate nanometer sheet in carbon fiber surface in-situ preparation, binding force is good；
2) carbon fiber loaded lithium titanate nanometer sheet is as flexible self-supporting negative electrode material, without using traditional lithium-ion battery
Metal collector, conductive additive and the binder that must be used in cathode preparation process, and without complicated electrode slice production
Process；
3) lamellar spacing of lithium titanate nanometer sheet is 0.2 ~ 0.6 μm, is evenly coated at carbon fiber surface, while being had good
Electric conductivity and ionic conductivity, therefore show higher battery specific capacity and high rate performance；
4) the carbon fiber loaded lithium titanate nanometer sheet obtained using method provided by the invention is due to carbon cloth substrate
Supporting role can arbitrarily be bent, folds and stretch, and can be used for the negative electrode material of flexible, foldable and scalable battery.
Detailed description of the invention
Fig. 1 is provided in an embodiment of the present invention to prepare carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode material
Flow chart.
Fig. 2 is the scanning of the carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode material obtained by the present embodiment 1
Electromicroscopic photograph (500 times).
Fig. 3 is the scanning of the carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode material obtained by the present embodiment 1
Electromicroscopic photograph (10000 multiplying power).
Fig. 4 is the circulation of the carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode material obtained by the present embodiment 1
Volt-ampere curve figure (scanning speed: 1 mv s).
Fig. 5 is the carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode material that is obtained by the present embodiment 1 in difference
Specific capacity and coulombic efficiency curve under multiplying power.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.Embodiment
In particular technique or condition person is not specified, described technology or conditions or according to the description of product according to the literature in the art
Book carries out.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.
S1: by carbon cloth in 300 ~ 400 DEG C of air calcination 20min, remove spare after the colloidal substance on surface；
S2: butyl titanate or isopropyl titanate, lithium hydroxide and hydrogen peroxide are dissolved in appropriate amount of deionized water by certain mol proportion
In, it is then transferred in polytetrafluoroethylcontainer container；
S3: being placed in carbon cloth is adherent in polytetrafluoroethylcontainer container, then under closed environment 140 ~ 160 DEG C of reactions 4 ~
8h；
S4: carbon cloth is taken out, and is dried after rinsing out surface adhesion particle with deionized water；
S5: it will be heat-treated 3 ~ 5h at a temperature of the carbon cloth of drying under inert gas protection 500 ~ 700 DEG C, obtains carbon fiber
Tie up the composite negative pole material of coated with uniform lithium titanate nanometer sheet.
In step sl, the carbon fiber can be polyacrylonitrile-radical, asphaltic base, viscose glue base or phenolic aldehyde base carbon fibre it
Any one of, fiber cloth can be non-woven fabrics or woven cloth；
In step sl, it is 300 ~ 400 DEG C that the carbon fiber, which removes glue temperature, and heating rate is 4 DEG C/min, air gas
Atmosphere, calcination time are 20 min；
In step s 2, molar ratio be butyl titanate or isopropyl titanate: lithium hydroxide: hydrogen peroxide=1:4 ~ 5:5,
The concentration of hydrogen peroxide is 30%；
In step s 2, the dosage of the deionized water is that 50 ~ 70ml of deionized water is added in every 2ml butyl titanate；
In step s3, the heat treatment can carry out under the inert gas shieldings such as argon gas or nitrogen, can also be
It being carried out under vacuum condition, the heating rate of heat treatment is 2 DEG C/min, and heat treatment temperature is 500 ~ 700 DEG C, heat treatment time is 3 ~
5h。
Embodiment 1:
By carbon cloth (polyacrylonitrile-based carbon fibre non-woven fabrics) (from room temperature with the heating of 4 DEG C/min in 300 DEG C of air
Rate rises to 300 DEG C) calcination 20min, it removes spare after the colloidal substance on surface；By butyl titanate, lithium hydroxide and hydrogen peroxide
In molar ratio 1:4:5 be dissolved in appropriate amount of deionized water (dosage of the deionized water be every 2ml butyl titanate be added deionized water
In 50ml), it is then transferred in polytetrafluoroethylcontainer container；It is placed in carbon cloth is adherent in polytetrafluoroethylcontainer container, so
140 DEG C of reaction 4h under closed environment afterwards；Carbon cloth is taken out, is dried after rinsing out surface adhesion particle with deionized water；
By 500 DEG C under inert gas protection of the carbon cloth of drying (rising to this temperature from room temperature with the heating rate of 2 DEG C/min) temperature
Degree is lower to be sintered 4h, obtains the flexible self-supporting negative electrode material that carbon fiber surface is uniformly coated with lithium titanate nanometer sheet.
Referring to figure 2. and Fig. 3, Fig. 2 and Fig. 3 are the carbon fiber loaded lithium titanate nanometer sheet 500 obtained by the present embodiment
Stereoscan photograph with 10000 times again.From the figure, it can be seen that the carbon fiber for having loaded lithium titanate nanometer sheet with a thickness of
7.5 μm, 7 μm of carbon fiber diameter are deducted, the thickness of lithium titanate nanometer sheet is about 0.25 μm, and Load Balanced.Lithium titanate nanometer sheet
It is evenly distributed on carbon fiber surface, there is good bond strength.Fig. 4 is the carbon fiber loaded lithium titanate obtained by the present embodiment
The cyclic voltammetry curve of the button cell of nanometer sheet flexible self-supporting negative electrode material assembling, the curve embody typical lithium titanate
Removal lithium embedded peak, illustrate carbon fiber surface obtain be lithium titanate nanometer sheet.Fig. 5 is to be born by the carbon fiber that the present embodiment obtains
Carry specific capacity and coulombic efficiency curve of the button cell of lithium titanate nanometer sheet flexible self-supporting cathode assembling under different multiplying.
Wherein zero discharge capacity is represented, ● black circle represents charging capacity, and ◇ represents coulombic efficiency.It is computed, prepared is flexible from branch
Support negative electrode material can still keep the specific capacity of 110mAh/g or more at 30C (1C=175mA/g), it was demonstrated that at the same have it is very good
Specific capacity and high rate performance.
Embodiment 2:
By carbon cloth (asphalt base carbon fiber non-woven fabrics) (from room temperature with the heating rate of 4 DEG C/min in 360 DEG C of air
Rise to 360 DEG C) calcination 20min, it removes spare after the colloidal substance on surface；Butyl titanate, lithium hydroxide and hydrogen peroxide are massaged
You than 1:4.5:5 be dissolved in appropriate amount of deionized water (dosage of the deionized water be every 2ml butyl titanate be added deionized water
In 60ml), it is then transferred in polytetrafluoroethylcontainer container；It is placed in carbon cloth is adherent in polytetrafluoroethylcontainer container, so
160 DEG C of reaction 5h under closed environment afterwards；Carbon cloth is taken out, is dried after rinsing out surface adhesion particle with deionized water；
By 550 DEG C under inert gas protection of the carbon cloth of drying (rising to this temperature from room temperature with the heating rate of 2 DEG C/min) temperature
Degree is lower to be sintered 5h, obtains the flexible self-supporting negative electrode material that carbon fiber surface is uniformly coated with lithium titanate nanometer sheet.It is obtained
The crystallization degree of carbon fiber loaded lithium titanate nanometer sheet is higher, specific capacity when 30C (1C=175mA/g) reach 120mAh/g with
On.
Embodiment 3:
By carbon cloth (viscose-based carbon fiber non-woven fabrics) (from room temperature with the heating rate of 4 DEG C/min in 400 DEG C of air
Rise to 400 DEG C) calcination 20min, it removes spare after the colloidal substance on surface；Butyl titanate, lithium hydroxide and hydrogen peroxide are massaged
You are dissolved in appropriate amount of deionized water than 1:5:5 (dosage of the deionized water is that deionized water 70ml is added in every 2ml butyl titanate)
In, it is then transferred in polytetrafluoroethylcontainer container；It is placed in carbon cloth is adherent in polytetrafluoroethylcontainer container, then close
The lower 150 DEG C of reactions 6h in closed loop border；Carbon cloth is taken out, is dried after rinsing out surface adhesion particle with deionized water；It will drying
700 DEG C under inert gas protection of carbon cloth (rising to this temperature from room temperature with the heating rate of 2 DEG C/min) at a temperature of burn
3h is tied, the flexible self-supporting negative electrode material that carbon fiber surface is uniformly coated with lithium titanate nanometer sheet is obtained.Obtained carbon fiber
Load that lithium titanate nanometer sheet is substantially the same manner as Example 1, specific capacity when 30C (1C=175mA/g) reaches 110mAh/g or more.
Embodiment 4:
By carbon cloth (asphalt base carbon fiber non-woven fabrics) (from room temperature with the heating rate of 4 DEG C/min in 350 DEG C of air
Rise to 400 DEG C) calcination 20min, it removes spare after the colloidal substance on surface；Isopropyl titanate, lithium hydroxide and hydrogen peroxide are massaged
You than 1:4.2:5 be dissolved in appropriate amount of deionized water (dosage of the deionized water be every 2ml butyl titanate be added deionized water
In 550ml), it is then transferred in polytetrafluoroethylcontainer container；It is placed in carbon cloth is adherent in polytetrafluoroethylcontainer container, so
145 DEG C of reaction 7h under closed environment afterwards；Carbon cloth is taken out, is dried after rinsing out surface adhesion particle with deionized water；
By 600 DEG C under inert gas protection of the carbon cloth of drying (rising to this temperature from room temperature with the heating rate of 2 DEG C/min) temperature
Degree is lower to be sintered 4.5h, obtains the flexible self-supporting negative electrode material that carbon fiber surface is uniformly coated with lithium titanate nanometer sheet.It is acquired
Carbon fiber loaded lithium titanate nanometer sheet it is substantially the same manner as Example 1, specific capacity when 30C (1C=175mA/g) reaches
110mAh/g or more.
Embodiment 5:
By carbon cloth (phenolic aldehyde base carbon fibre woven cloth) in 320 DEG C of air (from room temperature with the heating rate liter of 4 DEG C/min
To 400 DEG C) in calcination 20min, remove spare after the colloidal substance on surface；Butyl titanate, lithium hydroxide and hydrogen peroxide are massaged
You than 1:4.8:5 be dissolved in appropriate amount of deionized water (dosage of the deionized water be every 2ml butyl titanate be added deionized water
In 65ml), it is then transferred in polytetrafluoroethylcontainer container；It is placed in carbon cloth is adherent in polytetrafluoroethylcontainer container, so
155 DEG C of reaction 8h under closed environment afterwards；Carbon cloth is taken out, is dried after rinsing out surface adhesion particle with deionized water；
By 650 DEG C under inert gas protection of the carbon cloth of drying (rising to this temperature from room temperature with the heating rate of 2 DEG C/min) temperature
Degree is lower to be sintered 3.5h, obtains the flexible self-supporting negative electrode material that carbon fiber surface is uniformly coated with lithium titanate nanometer sheet.This implementation
Example is substantially the same manner as Example 1, the difference is that, heat treatment temperature is 580 DEG C.Obtained carbon fiber loaded lithium titanate is received
The crystallization degree of rice piece is higher, and specific capacity when 30C (1C=175mA/g) reaches 100mAh/g or more.
Embodiment 6:
By carbon cloth (polyacrylonitrile-based carbon fibre woven cloth) in 380 DEG C of air (from room temperature with the heating speed of 4 DEG C/min
Rate rises to 400 DEG C) in calcination 20min, remove spare after the colloidal substance on surface；By butyl titanate, lithium hydroxide and hydrogen peroxide
In molar ratio 1:4:5 be dissolved in appropriate amount of deionized water (dosage of the deionized water be every 2ml butyl titanate be added deionized water
In 68ml), it is then transferred in polytetrafluoroethylcontainer container；It is placed in carbon cloth is adherent in polytetrafluoroethylcontainer container, so
140 DEG C of reaction 6h under closed environment afterwards；Carbon cloth is taken out, is dried after rinsing out surface adhesion particle with deionized water；
By 500 DEG C under inert gas protection of the carbon cloth of drying (rising to this temperature from room temperature with the heating rate of 2 DEG C/min) temperature
Degree is lower to be sintered 5h, obtains the flexible self-supporting negative electrode material that carbon fiber surface is uniformly coated with lithium titanate nanometer sheet.It is obtained
The crystallization degree of carbon fiber loaded lithium titanate nanometer sheet is high, and specific capacity when 30C (1C=175mA/g) reaches 100mAh/g or more.
The crystallization degree of obtained carbon fiber loaded lithium titanate nanometer sheet is high, specific capacity when 30C (1C=175mA/g)
Reach 100mAh/g or more.
Note that the above is only a better embodiment of the present invention and the applied technical principle.It will be appreciated by those skilled in the art that
The invention is not limited to the specific embodiments described herein, be able to carry out for a person skilled in the art it is various it is apparent variation,
It readjusts and substitutes without departing from protection scope of the present invention.Therefore, although being carried out by above embodiments to the present invention
It is described in further detail, but the present invention is not limited to the above embodiments only, without departing from the inventive concept, also
It may include more other equivalent embodiments, and the scope of the invention is determined by the scope of the appended claims.
Claims (2)
1. a kind of carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode active material, which is characterized in that the flexibility
Self-supporting negative electrode material includes the lithium titanate nanoscale twins of carbon fiber and its surface in situ growth, the lithium titanate nanoscale twins thickness
It is 0.2~0.6 μm, and does not need using metal collector and binder；
The preparation method of the carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode active material is following steps:
S1: by carbon cloth in 300~400 DEG C of air calcination 20min, with guarantee carbon fiber not ablation and except glue it is thorough, institute
State the non-woven fabrics or woven cloth that carbon cloth is polyacrylonitrile-radical, asphaltic base, viscose glue base or phenolic aldehyde base carbon fibre；
S2: butyl titanate or isopropyl titanate, lithium hydroxide and hydrogen peroxide are dissolved in deionized water, are then transferred to poly- four
In vinyl fluoride container；
S3: being placed in above-mentioned gained carbon cloth is adherent in above-mentioned polytetrafluoroethylcontainer container, then 140 under closed environment~
160 DEG C of 4~8h of reaction, selected temperature range are suitble to lithium titanate nanometer sheet in the growth of carbon fiber surface, and selected time range is used
To adjust growth thickness；
S4: carbon cloth is taken out, and is dried after rinsing out surface adhesion particle with deionized water；
S5: the carbon cloth of above-mentioned drying is heat-treated at a temperature of 500~700 DEG C under inert gas protection or under vacuum condition
3~5h obtains carbon fiber loaded lithium titanate nanometer sheet flexible self-supporting negative electrode material.
2. a kind of battery, including anode, cathode and electrolyte, which is characterized in that the cathode includes according to described in claim 1
Carbon fiber loaded lithium titanate nanometer sheet negative electrode active material；The titanium of the carbon fiber loaded lithium titanate nanometer sheet negative electrode active material
Sour lithium nanoscale twins are evenly coated at carbon fiber surface.
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| CN107681170A (en) * | 2017-10-12 | 2018-02-09 | 惠州市金能源科技有限公司 | Scalable zinc-manganese cell and preparation method of anode thereof |
| CN109065840A (en) * | 2018-07-13 | 2018-12-21 | 惠州市智键科技有限公司 | A kind of based lithium-ion battery positive plate and preparation method thereof |
| CN109659497A (en) * | 2019-01-30 | 2019-04-19 | 青岛大学 | A kind of preparation method of the flexible metatitanic acid lithium electrode based on carbon cloth |
| CN109873114A (en) * | 2019-02-26 | 2019-06-11 | 常熟理工学院 | A kind of flexible compound membrane electrode material of high initial coulomb efficiency and preparation method thereof |
| CN110137441B (en) * | 2019-02-28 | 2021-03-26 | 厦门理工学院 | Carbon fiber in-situ loaded gallium nitride negative electrode material, preparation method and lithium ion battery |
| CN113659127A (en) * | 2021-08-19 | 2021-11-16 | 电子科技大学长三角研究院(湖州) | Carbon nanofiber/lithium titanate composite electrode material and preparation method and application thereof |
| CN114975868A (en) * | 2022-06-06 | 2022-08-30 | 同济大学 | Dual-ion battery positive electrode, preparation method and dual-ion battery comprising same |
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| CN105789582A (en) * | 2016-03-25 | 2016-07-20 | 华东理工大学 | Lithium titanate/porous carbon composite material and preparation method of lithium titanate/porous carbon composite material |
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| CN102623704A (en) * | 2012-03-26 | 2012-08-01 | 上海大学 | Preparation method of lithium titanate-carbon fiber composite material for cathode of lithium ion battery |
| CN103531756A (en) * | 2013-11-01 | 2014-01-22 | 北京化工大学 | Carbon nanofiber loaded lithium titanate thin film materials and manufacturing method thereof |
| CN104600266A (en) * | 2015-01-09 | 2015-05-06 | 上海大学 | Method for preparing carbon fibre cloth loaded sulphur composite material |
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